TW200804460A - A process for the production of phenylene ether olygomer - Google Patents
A process for the production of phenylene ether olygomer Download PDFInfo
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- TW200804460A TW200804460A TW96118689A TW96118689A TW200804460A TW 200804460 A TW200804460 A TW 200804460A TW 96118689 A TW96118689 A TW 96118689A TW 96118689 A TW96118689 A TW 96118689A TW 200804460 A TW200804460 A TW 200804460A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
Abstract
Description
200804460 九、發明說明： 【發明所屬之技術領域】 本發明有關於一種提高對各種溶劑類的溶解性及與其 • 他樹脂類的相溶性之二苯醚低聚物之製造方法。 . 【先前技術】 現在，南分子量二苯醚化合物例如聚二苯醚樹脂（以後 簡稱為PPE，例如日本專利特公昭42— 3195號公報、特 公昭58— 53012號公報），因顯示優異之高頻特性、耐熱 性及難燃性，故適用於電氣/電子材料用途或構造材料用 迷等。即，PPE具有其優異之特性’同時視用途具有易對 官能基進行修飾之酚性羥基。然而，由於在電氣/電子材 料領域所使用之環氧樹脂或氰酸酯樹脂等與熱硬化性樹 脂等的相溶性差、對通用溶劑的溶解性欠佳、又與在構造 材料等中所使用的其他塑膠的相溶性差等原因，故而限定 了其使用範圍’無法在多方面發揮其優異特性。因此，為 • 了擴大=PE的使用範圍，例如提出有與氰酸酯樹脂進行 IPN( ^ f ^ ^ ^ ^ ^ ^ , interpenetrating polymer network)構造化之方法（例如日本專利第32㈣π號公 報）、利用自由基觸媒使高分子量ppE較低分子量化之方 $ (例如日本專利第3248424號公報）、或者將二元酚化合 $與-元驗化合物進行氧化聚合之方法（例如日本專利特 二^ 8 011747號公報）等。又，亦對將特定的雙盼化合 =特定的-元紛化合物進行氧化聚合而製造二苯鍵低 之方法（例如日本專利特開2003- 12796號公報）進 312XP/發明說明書(補件)/96-09/96118689 c 200804460 =了研究，但利用該方法製造之二苯醚低聚物難以粒子狀 態析出，於工業製造中則成為問題。 即通¥聚—苯鍵樹脂係於芳香族烴溶液中獲得，再於 •甲=等醇類中進行粒子化，但若將相同方法應用於二苯鱗 低艰物，則低分子量體會高效率地溶解於甲醇等醇類中而 無法獲得粒子。又，當為了降低二苯醚低聚物在醇類中的 溶解度而添加水時，發現有黏稠物析出，因而 適用於工業生產。 _【發明内容】 (發明所欲解決之問題） 本么明之目的在於提供一種二苯醚低聚物之工業製造 方法’其係於發揮二苯醚構造之優異的電氣特性:、耐熱 性、難燃性之特徵，進而與其他樹脂的相溶性及對通用溶 劑的溶解性為顯著址古 〜_貝者地呵，具有視用途容易進行修飾的酚性 經基之一本驗低聚物之製造中 以粒子狀態析出。^中，可以地使二苯_低聚物 (解決問題之手段） 本啦明者們赛於上述課韻隹 k硃碡進仃了努力研究，結果於 因所得二苯醚低聚物斟古德、口木^現· ㈣本物對有機溶劑的溶解性過高，m中 二苯醚低聚物的芳香族徊^現』猎由將 采浐、hf丨一 ^谷劑溶液暫時置換成沸點較芳 曰族k/谷劑南的水溶性右 方 低聚物以粒子狀態析出：躅而使-本鞑 烴溶劑、藉由粒子化而排出 換的方曰無 勺/慮液中所含的水溶性有機溶 312XP/發明說明書(補件)/96,09/96118689 6 200804460 醇子中所含的水溶性有機溶劑除去，故可將所使 用私類加以回收、再利用。 =月提供一種二苯鍵低聚物之製造方法，其係於將以 的二㈣化合物與以通式⑵^的一元盼 止i t 溶财進行氧化聚合者；於聚合反應停 族烴溶劑高的水溶性有機溶劑 —換成乂方曰 u ^ m ^ 4 使一本醚低聚物溶液與 水接觸而使二苯醚低聚物以粒子狀態析出。 夕進〜”月提供一種將所使用有機溶劑等加以再利用 之一本醚低聚物之製造方法。 [化1] R1 R3 R5 R7200804460 IX. OBJECTS OF THE INVENTION: 1. Field of the Invention The present invention relates to a method for producing a diphenyl ether oligomer which improves solubility in various solvents and compatibility with other resins. [Prior Art] Now, a south molecular weight diphenyl ether compound such as a polydiphenyl ether resin (hereinafter, abbreviated as PPE, for example, Japanese Patent Publication No. Sho 42-3195, Japanese Patent Publication No. SHO 58-53012) is excellent in display performance. Frequency characteristics, heat resistance and flame retardancy, it is suitable for use in electrical/electronic materials or construction materials. Namely, PPE has its excellent characteristics. At the same time, it has a phenolic hydroxyl group which is easy to modify a functional group depending on the use. However, the epoxy resin, the cyanate resin, and the like used in the field of electrical/electronic materials are inferior in compatibility with a thermosetting resin or the like, have poor solubility in a general-purpose solvent, and are used in construction materials and the like. Because of the poor compatibility of other plastics, etc., the scope of use is limited, and it is not possible to exert its excellent characteristics in many aspects. Therefore, in order to expand the range of use of PE, for example, a method of constructing IPN ( ^ f ^ ^ ^ ^ ^ , interpenetrating polymer network) with a cyanate resin has been proposed (for example, Japanese Patent No. 32 (four) π Bulletin), A method of lowering the molecular weight of a high molecular weight ppE by a radical catalyst (for example, Japanese Patent No. 3248424), or a method of oxidative polymerization of a dihydric phenol compounded with a -methine compound (for example, Japanese Patent Special 2) Bulletin No. 8 011747). In addition, a method of producing a diphenyl bond by oxidative polymerization of a specific dioxin compound to a specific ternary compound (for example, Japanese Patent Laid-Open Publication No. 2003-12976) is incorporated herein by reference. 96-09/96118689 c 200804460 = Research, but the diphenyl ether oligomer produced by this method is difficult to precipitate in a particulate state, which is a problem in industrial production. That is, the poly-benzene-bonded resin is obtained in an aromatic hydrocarbon solution, and then is subjected to particle formation in an alcohol such as A=, but if the same method is applied to diphenyl scales, the low molecular weight body will be highly efficient. The solution is dissolved in an alcohol such as methanol to obtain particles. Further, when water is added in order to lower the solubility of the diphenyl ether oligomer in the alcohol, it is found that a thick substance is precipitated, and thus it is suitable for industrial production. _ [Summary of the Invention] (Problems to be Solved by the Invention) The purpose of the present invention is to provide an industrial manufacturing method for a diphenyl ether oligomer which is excellent in electrical properties of a diphenyl ether structure: heat resistance and difficulty The characteristics of flammability, and further compatibility with other resins and solubility in general-purpose solvents are significant. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is precipitated in the state of particles. ^, can make diphenyl _ oligomers (the means to solve the problem) Benjamins in the above-mentioned class rhyme 隹 k Zhu Yujin diligently studied, the result of the resulting diphenyl ether oligomers (de) The solubility of the substance in the organic solvent is too high, and the aromatic oxime of the diphenyl ether oligomer in m is temporarily replaced by the boiling point of the picking and hf 丨 ^ ^ solution. The water-soluble right oligomer of the fang k k/ 谷 剂 South is precipitated in the form of particles: 躅 使 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑 鞑Water-soluble organic solvent 312XP / invention specification (supplement) / 96, 09/96118689 6 200804460 The water-soluble organic solvent contained in the alcohol is removed, so that the private type used can be recovered and reused. = month provides a method for producing a diphenyl bond oligomer, which is obtained by oxidative polymerization of a di(tetra) compound with a monovalent of the formula (2), and a high solvent in the polymerization reaction. The water-soluble organic solvent-exchanged into an anthracene 曰u ^ m ^ 4 allows a solution of the ether oligomer to be contacted with water to precipitate the diphenyl ether oligomer in a particulate state. In the evening, the method of producing one of the ether oligomers by reusing the organic solvent or the like is provided. [Chemical Formula 1] R1 R3 R5 R7
OHOH
(1) [化2] (2) R11 R9 R12 R10 (上述式中，Rl、R2、R3、R7、R8、R9、R10可相同或 者不同，表示鹵素原子或者碳數6以下之烷基或苯基； 312XP/發明說明書(補件)/96-09/96118689 η 200804460 Μ、R5、R6、RU、R12可相同或者不同，表示氫原子、 *素原子或者碳數6以下之烷基或苯基）。 (發明效果） 透過本發明’可工業性製造發揮二苯趟構造之優異之電 =特性、耐熱性、難燃性之特徵，進而與其他樹脂的相溶 =對通祕㈣溶解性為顯著地高，具有制途容易進 仃修飾的酚性羥基之二苯醚低 .„ — 本軋低來物，實現了向含有經末端(1) (2) (2) R11 R9 R12 R10 (In the above formula, R1, R2, R3, R7, R8, R9 and R10 may be the same or different and represent a halogen atom or an alkyl group having 6 or less carbon atoms or benzene. 312XP/Invention Manual (Supplement)/96-09/96118689 η 200804460 Μ, R5, R6, RU, R12 may be the same or different and represent a hydrogen atom, a * atom or an alkyl group having 6 or less carbon atoms or a phenyl group. ). (Effect of the Invention) The present invention can be industrially produced to exhibit the excellent electrical properties, heat resistance, and flame retardancy of the diphenylfluorene structure, and further compatible with other resins = to the secret (four) solubility is remarkable High, low-diphenyl ether with phenolic hydroxyl group which is easy to be modified in the process. „ —
土 的一本醚結構化合物等之展開。進而，藉由將芳夭 族烴溶劑、水溶性有機溶劑等加以回收、再利 ： 地供給二苯醚低聚物。 廉知 【實施方式】 本發明之二苯醚低聚物之製造方法 示的二元酚化合物與以通式（2 ) — ' 、 ^ ^ )表 香族烴溶射進行氧化聚合，—元雜合物於芳 [化3] 成二苯醚低聚物。 R1 R3 R5 R7The development of an ether structural compound of the earth. Further, a diphenyl ether oligomer is supplied by recovering an aromatic hydrocarbon solvent, a water-soluble organic solvent or the like. INTELLIGENCE [Embodiment] The dihydric phenol compound of the method for producing a diphenyl ether oligomer of the present invention is oxidatively polymerized by spraying a salient hydrocarbon of the formula (2) - ', ^ ^ ), and the element is heterozygous. The compound is a diphenyl ether oligomer. R1 R3 R5 R7
[化4] 312XP/發明說明書(補件)/96-09/96118689 (2) 200804460 R11 R9[Chemical 4] 312XP / invention manual (supplement) / 96-09/96118689 (2) 200804460 R11 R9
0H R12 Rl〇 本=明中所使用之所謂：⑽化合物，係指於通式⑴ ，、R2、K3、R7、R8為相同或者不同.，為鹵素 或者碳數“X下之院基或苯基，R4、R5、R6為相同或者 不同，為虱原子、鹵素原子或者碳數 戈 基，、“必須為氯々子：二=本 :單獨使用該二元紛化合物或者使用2種以上：混合 物。作為该二兀酚化合物，具體而言，以2 3 2%，3, ，_Λ苯）_4其二醇等為佳，特別以 ;圭。，，3’5,5_六甲基屮，1，-聯苯)-4,4’_二醇為更 本發明中所使用之利-元聽合物，於通式（， R9、R10可相同或者不同，為鹵素 炫基或笨基，可相同或者不:者=下： 素原子或者碳數6以下之烷基或苯基 用: 齡化合物或者使用2種類以上的混合物。特別以 於2, 6位具有置換基者、或者將其與於2 3 6位或m 6 位具有置換基者並用為佳。具體而言，以2 _ ，， 本舍明之二苯鱗低聚物之製造方法，與例如於曰本專利 312XP/發明說明書(補件)/96-09/96118689 9 200804460 特公昭42- 3195號公報、特公昭58_53〇12號公報 不PPE之製造方法同樣，係使用由金屬鹽與胺的組合所 成之觸媒，將以通式（1)表示的二元酚化合物與以通式（？） -表示的一元酚化合物進行氧化聚合而獲得二苯醚低聚 •物。此處所使用之金屬鹽之金屬，以銅或錳為佳，但以觸 媒活性高的銅為更佳。又，作為助觸媒，亦可將日本專利 特公昭58 - 53012號公報中例示之相間移動觸媒與由金 屬鹽與胺的組合所構成之觸媒合併使用。氧化聚合，係於 上述觸媒存在下利用氧氣而進行，可例示直接將氧氣導入 聚合容器内之方法、或者將被惰性氣體稀釋的氧氣導入聚 ^容器内之方法等，並無特別限^。將空氣以氮氣等惰性 氣體加以稀釋，將氧氣濃度調製成使用溶劑類的***極限 氧氣濃度範圍外再導入聚合容器内，此就安全方面之觀點 而言為較佳。 “ 氧化聚合之反應溶劑，係使用對氧化反應為安定之笨、 ⑩甲苯、二曱苯等芳香族烴。其中，就安全性以及蒸發除去 的合易性而言，以曱苯為佳。又，因所得二苯醚低聚物對 有機溶劑的溶解性良好，故聚合結束時於芳香族烴的重量 為總溶劑量的50%以上之範圍内，可將先前ppE的不良溶 - 劑中不適於用作反應溶劑的甲醇、乙醇等醇類，己烷、庚 ， 烷等脂肪族烴類，丙酮、曱基乙基酮等酮類，乙酸乙酯等 酯類，二甲基甲醯胺等醯胺類等用於聚合。特別是當將 2, 2’，3, 3’，5, 5’ _六曱基-（1，Γ -聯苯）-4, 4,-二醇使用於 二元紛化合物時，以將比較好地溶解2, 2,，3, 3,，5, 5,-六 312XP/發明說明書(補件)/96〇9/96i丨8腳 1〇 200804460 曱基-(1，Γ -聯苯）-4, 4’ -二醇的甲醇與芳香族烴混合後 使用為佳。 於本發明中，對於以通式（1)表示的二元酚化合物與以 一 通式（2)表示的一元紛化合物進行氧化聚合之方法，並無 特別限定。作為一般性方法，可例示：將二元酚化合物與 一元酚化合物一次性投入聚合容器後，一面吹入含氧氣體 一面進行氧化聚合之方法；一面吹入含氧氣體一面將二元 盼化合物與一元盼化合物連續地投入聚合容器而進行氧 _化聚合之方法；或者預先將二元酚化合物與一元酚化合物 與由金屬鹽及胺所構成的觸媒混合，然後連續地投入聚合 容器進行氧化聚合之方法。對於本發明之製造方法之聚合 溫度，並無特別限定。一般而言，較佳為10〜60°C，更 佳為20〜50°C。若聚合溫度低則必須具有將聚合容器冷 卻之特別的附帶裝置，因而就經濟性而言欠佳。又，若聚 合溫度高則必須具有將聚合容器加熱的附帶裝置，此外排 _出氣體中所含的溶劑蒸氣量增加，因此使進行冷卻並將溶 劑凝縮回收之裝置中之負荷增加，故而欠佳。該聚合反應 係發熱反應，為了將系統内溫度控制在一定範圍内，必須 對聚合反應溶液進行除熱處理。除熱中，可使用聚合容器 . 夾套或者外部循環熱交換器。又，可利用吹入用於氧化反 _ 應的聚合容器内的含氧氣體的排出氣體中所含溶劑之蒸 發潛熱，進行聚合容器内的除熱。更佳的是，可藉由於反 應溶劑中加入蒸發潛熱高的醇類，而同時提高排出氣體及 蒸發溶劑之除熱效果。 312XP/發明說明書(補件)/96-09/96118689 11 200804460 於本發明中，藉由將通式（1 )表示的二元酚化合物與以 通式（2)表示的一元酚化合物進行氧化聚合而獲得之二笨 醚低聚物，其主成分係以通式（3)表示之化合物，含=以 通式（4)表示之化合物作為副產物。 [化5]0H R12 Rl 〇 = = = = = ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The group, R4, R5, and R6 are the same or different and are a halogen atom, a halogen atom or a carbon number, and "must be a chlorine raft: two = this: use the binary compound alone or use two or more kinds: a mixture . As the dihydric phenol compound, specifically, diol or the like is preferably 2 2 2%, 3, and benzene benzene), and the like is particularly preferred. ,, 3'5,5-hexamethylguanidinium, 1,2-biphenyl)-4,4'-diol is a leuco-audio compound used in the present invention, in the formula (R9, R10) They may be the same or different and may be the same as halogen or phenyl group, and may be the same or not: = lower: a single atom or an alkyl group having a carbon number of 6 or less or a phenyl group: an aged compound or a mixture of two or more types. It is preferred to use a substituent having 2 or 6 positions, or a substituent having a substitution base at 2 3 6 or m 6 . Specifically, the production of a diphenyl scale oligomer of 2 _ , Benbenming The method is the same as the manufacturing method of the non-PPE, as in the method of manufacturing the non-PPE, for example, in the patent 312XP/invention specification (supplement)/96-09/96118689 9 200804460, the public publication No. Sho 42- 3195, and the Japanese Patent Publication No. 58-53〇12. A catalyst formed by a combination of a salt and an amine is obtained by oxidative polymerization of a dihydric phenol compound represented by the formula (1) and a monohydric phenol compound represented by the formula (?) - to obtain a diphenyl ether oligomeric material. The metal of the metal salt used herein is preferably copper or manganese, but copper having a high catalytic activity is more preferable. Also, as a catalyst, The interphase moving catalyst exemplified in Japanese Patent Publication No. Sho 58-53012 can be used in combination with a catalyst composed of a combination of a metal salt and an amine. Oxidative polymerization can be carried out by using oxygen in the presence of the above catalyst. The method of directly introducing oxygen into the polymerization vessel or the method of introducing oxygen diluted by the inert gas into the polymerization vessel is not particularly limited. The air is diluted with an inert gas such as nitrogen to prepare the oxygen concentration for use. The solvent is explosively introduced into the polymerization vessel outside the oxygen concentration range, which is preferable from the viewpoint of safety. "The reaction solvent for oxidative polymerization is stabilized by oxidation, 10 toluene, diphenylbenzene. In particular, aromatic hydrocarbons are preferred in terms of safety and ease of evaporation. Further, since the obtained diphenyl ether oligomer has good solubility in an organic solvent, the polymerization is terminated at the end of the fragrance. The weight of the hydrocarbon is in the range of 50% or more of the total solvent amount, and an alcohol such as methanol or ethanol which is not suitable as a reaction solvent in the poor solvent of the previous ppE can be used. An aliphatic hydrocarbon such as hexane, heptane or alkane; a ketone such as acetone or mercaptoethyl ketone; an ester such as ethyl acetate; an amide such as dimethylformamide or the like, which is used for polymerization. , 2',3,3',5,5' _hexamethylene-(1, fluorene-biphenyl)-4,4,-diol is used in a binary compound to dissolve better 2 2,,3,3,,5,5,-six 312XP/invention manual (supplement)/96〇9/96i丨8-foot 1〇200804460 曱基-(1,Γ-biphenyl)-4, 4' - The methanol of the diol is preferably used after mixing with an aromatic hydrocarbon. In the present invention, the method of oxidative polymerization of a dihydric phenol compound represented by the general formula (1) and a monovalent compound represented by the general formula (2) There is no special limit. As a general method, a method in which a dihydric phenol compound and a monohydric phenol compound are once put into a polymerization vessel and then oxidatively polymerized while blowing an oxygen-containing gas can be exemplified; A method in which a compound is continuously supplied to a polymerization vessel for oxygen-polymerization; or a dihydric phenol compound and a monohydric phenol compound are mixed with a catalyst composed of a metal salt and an amine, and then continuously introduced into a polymerization vessel for oxidative polymerization. The method. The polymerization temperature in the production method of the present invention is not particularly limited. In general, it is preferably 10 to 60 ° C, more preferably 20 to 50 ° C. If the polymerization temperature is low, it is necessary to have a special accessory device for cooling the polymerization vessel, which is not economically preferable. Further, when the polymerization temperature is high, it is necessary to have an accessory device for heating the polymerization vessel, and the amount of the solvent vapor contained in the exhaust gas is increased. Therefore, the load in the apparatus for cooling and recovering the solvent is increased, so that it is not preferable. . The polymerization reaction is an exothermic reaction, and in order to control the temperature in the system within a certain range, the polymerization reaction solution must be subjected to heat treatment. In addition to heat, a polymerization vessel can be used. Jacket or external circulation heat exchanger. Further, the latent heat of vaporization of the solvent contained in the exhaust gas of the oxygen-containing gas blown into the polymerization vessel for oxidizing the reaction can be used to remove heat in the polymerization vessel. More preferably, the heat removal effect of the exhaust gas and the evaporating solvent can be improved by adding an alcohol having a high latent heat of vaporization to the reaction solvent. 312XP/Invention Specification (Supplement)/96-09/96118689 11 200804460 In the present invention, oxidative polymerization of a dihydric phenol compound represented by the general formula (1) and a monohydric phenol compound represented by the general formula (2) is carried out. The diphenyl ether oligomer obtained has a main component represented by the formula (3) and contains a compound represented by the formula (4) as a by-product. [Chemical 5]
[化6] Η[化6] Η
(4) 上述式中，ΙΠ、R2、R3、R7、R8、R9、R1〇可相同或者 不同，表示i素原子或者碳數6以下之烷基或苯基eR4、 R6、R1卜R12可相同或者不同，表示氫原子、鹵素 原子或者碳數6以下之烷基或苯基。m、n至少任一個不 為〇,表示0〜25之整數，1表示1〜5〇之整數。 本發明中所得二苯醚低聚物之數量平均分子量，以5〇〇 〜5j)00為佳，特別以500〜3〇〇〇為更佳。若數量平均分 子1丨、於孩範圍，則作為低聚物之收率較低，又，若數量 312XP/發明說明書(補件)/96·09/96118689 ι2 200804460 :均分子量大於該範圍’則在通用溶财之溶解性差 月書中記述之所謂數量平均分子量，係使用凝膠 析儀(以後簡稱GPC)，求出標準聚苯乙焊的溶出時 =準聚苯乙稀分子量之關聯，求出與二苯， ㈣應的聚苯乙稀分子量，而作為聚苯乙稀換Ϊ 數1平均分子量加以定義。 π 制=:元紛化合物與二元紛化合物之調配比例，則可 衣w不子量之二苯㈣聚物。當—元龄化合物多於二 =化合物時’二苯醚低聚物之分子量增力”可任意決定 :紛化合物與二元盼化合物之調配比例，但較佳的是， =二苯㈣聚物的數量平均分子量成為州〜漏，特別 :成為500〜3_之方式進行調配。具體而言，一元酚化 ^勿與二⑽化合物之調配比例，若以（―元聽合物莫 耳）/( 一 70酚化合物莫耳數）來表示，則以2(莫耳/莫耳） 〜30(莫耳/莫耳）為佳。 口：本發明之二苯鱗低聚物之製造方法中，於氧化聚合過 矛.有吟冒生成與所使用原料不同之結構。具體可舉 2附f7有甲氧基、絲、幾基、觸媒中所使用胺類之結 该等異種結構之生成，無法獲得氧化反應的停止， 但若相對於原料酚置換基的總莫耳數為1〇莫耳％以下、更 佳為5莫耳心下，關料影#所得二苯⑽低聚物之物 於本1明中，自於氧化聚合中所得二苯鱗低聚物的聚合 反應溶液中除去金屬鹽以使聚合反應停止，而形成二苯醚 312XP/發明說明書(補件)/96-09/96118689 13 200804460 ，溶液。此時’較佳的是，使螯合劑水溶液盘 ^谷液接觸而將金屬鹽萃取至水溶液侧。作為螯合^若 形成錯合物並將觸媒金屬向水相：萃取 =劑：㈣別限制。作為較佳的整合劑水溶液，可 牛乙-胺四乙酸的驗金屬鹽之水溶液、或者乙二胺四 液n 物之水溶液；作為更佳的螯合劑水溶 一 不.乙—胺四乙酸二鈉、乙二胺四乙酸三鈉、乙 丨四乙酸四鈉水溶液。接觸時間，若水溶液為均勻分散 =則㈣相為佳，為1分㈣上、較料5分鐘以上 此¥之溫度’可為不使二苯醚低聚物自聚合反應溶液中析 出、’=劑不錢之溫度範圍。通常於聚合反應溫度土阶 下進仃接觸’無需設置過大的冷卻或加熱設備，故為較佳。 、:將水冷性有機溶劑與芳香族烴溶劑混合而作為反應 溶劑使用時’聚合反應溶液中所含的水溶性有機溶劑之全 π或-部分亦被萃取至水溶液侧。t於聚合反應中將水溶 性有機溶劑混合而使料，亦應注意將水溶性有機溶劑萃 取後的螯合劑水溶液的比重，合劑水溶液接觸後的聚合 反應溶液與螯合劑水溶液之比重差，較佳為0 001以上， =佳為G.G1以上。若螯合劑水溶液的比重小於聚合反應 /合液的比ΐ ’則使水溶液成為輕液，又若聲合劑水溶液的 比重大於聚合反應溶液的比重，則使水溶液成為重液，從 而可進行液液分離。二苯醚低聚物的聚合反應溶液與螯合 劑水溶液之分離，係可於停止聚合反應溶液與螯合劑水溶 液的混合接觸之後，靜置而分離。為了縮短時間，以使用 312沿/發明說明書(補件)/96-09/96118689 14 200804460 連續式或批次式離心分離型液液分離裝置或聚結器 (coalescer)等過濾器型液液分離裝置為佳。 繼而，較佳的是，使與螯合劑水溶液接觸後的二苯醚低 聚物的聚合反應溶液與水接觸，而將殘留於聚合反應溶液 中的少量金屬鹽萃取出。聚合反應溶液與冰之分離，可自(4) In the above formula, ΙΠ, R2, R3, R7, R8, R9, and R1〇 may be the same or different and each represents an i atom or an alkyl group having 6 or less carbon atoms or a phenyl group eR4, R6, and R1 may be the same. Alternatively, it may represent a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms or a phenyl group. At least one of m and n is not 〇, and represents an integer of 0 to 25, and 1 represents an integer of 1 to 5 。. The number average molecular weight of the diphenyl ether oligomer obtained in the present invention is preferably from 5 Å to 5 Å 00, particularly preferably from 500 to 3 Å. If the number average molecule is 1丨, the yield of the oligomer is lower, and if the quantity is 312XP/invention specification (supplement)/96·09/96118689 ι2 200804460: the average molecular weight is larger than the range' The so-called number average molecular weight described in the book of Solubility of General Pharmacy is determined by using a gel analyzer (hereinafter referred to as GPC) to determine the molecular weight of the standard polystyrene welding = the molecular weight of the quasi-polystyrene. The molecular weight of polystyrene which is related to diphenyl, (iv), and the average molecular weight of polyphenylene is changed as the number of polystyrene. π system =: The proportion of the compound and the binary compound can be used to coat the diphenyl (tetra) polymer. When the number of the compound is more than two = compound, the molecular weight of the diphenyl ether oligomer can be arbitrarily determined: the ratio of the compound to the binary compound, but preferably, the diphenyl (tetra) polymer The number average molecular weight becomes state-to-leak, in particular: it is formulated in a manner of 500~3_. Specifically, the ratio of monobasic phenolation to the compound of the two (10) compound, if (-------------) (A 70 phenol compound Molar number) is preferably 2 (mol/mole) ~ 30 (mol/mole). Port: In the method for producing a diphenyl scale oligomer of the present invention, The oxidative polymerization has a spear. It has a structure different from that of the raw materials used. Specifically, the formation of the heterostructures of the methoxy group, the silk, the several groups, and the amine used in the catalyst can be obtained. The cessation of the oxidation reaction cannot be obtained, but if the total number of moles relative to the starting phenol substituent is 1 〇 mol% or less, more preferably 5 moles, the diphenyl (10) oligomer obtained from the product In the present invention, the metal salt is removed from the polymerization reaction solution of the diphenyl scale oligomer obtained in the oxidative polymerization. In order to stop the polymerization, a diphenyl ether 312XP / invention specification (supplement) / 96-09/96118689 13 200804460, a solution is formed. At this time, it is preferred that the chelating agent aqueous solution is contacted with the liquid to the metal. The salt is extracted to the side of the aqueous solution. As a chelate, if a complex is formed and the catalyst metal is directed to the aqueous phase: extraction = agent: (4) is not limited. As a preferred aqueous solution of the integrator, the metal of the bovine-aminotetraacetic acid can be used. An aqueous solution of salt or an aqueous solution of ethylenediamine and four liquids; as a better chelating agent, water-soluble, disodium ethane-amine tetraacetate, trisodium ethylenediaminetetraacetate, tetrasodium acetate tetraacetate aqueous solution. Time, if the aqueous solution is uniformly dispersed = then the (four) phase is better, for 1 minute (four), for more than 5 minutes, the temperature of the ¥ can be such that the diphenyl ether oligomer does not precipitate from the polymerization solution, '= agent The temperature range of not being used. Usually, the contact is carried out under the soil temperature of the polymerization reaction temperature. Therefore, it is preferable to provide an excessive cooling or heating device. The water-cooling organic solvent is mixed with an aromatic hydrocarbon solvent and used as a reaction solvent. When 'polymerization solution The whole π or - part of the water-soluble organic solvent is also extracted to the side of the aqueous solution. The water-soluble organic solvent is mixed in the polymerization reaction to make the material, and the specific gravity of the chelating agent aqueous solution after extracting the water-soluble organic solvent should also be noted. The specific gravity difference between the polymerization solution after contact with the aqueous solution of the mixture and the aqueous solution of the chelating agent is preferably 0 001 or more, and preferably is higher than G.G1. If the specific gravity of the aqueous solution of the chelating agent is smaller than the ratio 聚合 of the polymerization reaction/liquid mixture, The aqueous solution becomes a light liquid, and if the specific gravity of the aqueous solution of the sounding agent is larger than the specific gravity of the polymerization reaction solution, the aqueous solution becomes a heavy liquid, thereby performing liquid-liquid separation. The separation of the polymerization reaction solution of the diphenyl ether oligomer and the aqueous solution of the chelating agent, After the polymerization reaction solution is stopped from contact with the aqueous solution of the chelating agent, it is allowed to stand and is allowed to stand. In order to shorten the time, use the filter type liquid-liquid separation such as the 312 edge/invention specification (supplement)/96-09/96118689 14 200804460 continuous or batch type centrifugal liquid-liquid separation device or coalescer The device is better. Then, it is preferred that the polymerization reaction solution of the diphenyl ether oligomer after contact with the aqueous solution of the chelating agent is brought into contact with water, and a small amount of the metal salt remaining in the polymerization reaction solution is extracted. Separation of the polymerization solution from ice, which can be
上述例示的與螯合劑的分離方法中選擇。對於接觸溫度以 及與水的分離溫度並無特別限制，但於4(rc以上、較佳 為80°C以上實施，可有效地縮短分離時間。進行丨次或 者重複2次以上該使用水之清洗。進行利用水之清洗，直 至二苯醚低聚物的聚合反應溶液中之觸媒金屬殘渣相對 於二苯醚低聚物為l〇〇y g/g以下、較佳為5〇#g/g以下、 更佳為ΙΟ/zg/g以下。又，最終水洗結束後之水的導電 度，以50mS/m以下為佳，以2〇mS/m以下為更佳。又，當 將水洗次數設為複數次時，可將第n次使用的水的一部^ 或全部於第（η-1)次水洗時循環使用。又，第i次水洗後 的水’不論水洗次數，可將其一部分或全部使用於對聚^ 停止中所使用螯合劑水溶液之調整。藉此，獲得本發明; 使用之二苯醚低聚物溶液。 其次’就將本發明之二苯鱗低聚物溶液的芳香族煙 置換成沸點較芳香族烴高的水溶性有機溶劑後，使二笨^ 低聚物溶液與水接觸而使二苯醚低聚物以粒 2 之步驟加以說明。於PPE之製造方法中，取 = 析來合反應澄、、念 直接與醇類接觸而獲得PPE粒子之方法係—般性方I / 因二苯醚低聚物的分子量低’故對芳香族烴與又醇的混合： 312XP/發明說明書(補件)/96_09/96118689 15 200804460 劑顯示溶解性。+ 接觸時，存在以下缺^^苯喊低聚物溶液直接與醇類 率低，而且產生，溶不卿子的收 赫。铒比 ,刀/合耆的黏稠物而難以進行固體分 置換《點較本芳發4::4,聚物溶液的芳香族經溶劑 的二笨鱗低聚物二::接=吏有機溶劑’並使置換後 #能批山 夜/、水接觸而使二苯醚低聚物以粒子 心 之方法，係解決與二苯醚低聚 的上述問題之方法。 口篮衣w有關 ☆背i置換中所使用的水溶性有機溶劑，其沸點高於反 應溶劑中所使㈣芳香族烴溶劑。具體而言，以二甲基 醯胺、N，N-二甲基乙醯胺或| N_甲基料咬酮、二^基 亞砜為佳，特別就處理容易性而言以N，N_二甲基乙醯ς 為更佳。溶劑置換，係預先將二苯醚低聚物溶液與水溶性 有機溶劑混合或者分別導入蒸餾裝置中，於大氣壓或減壓 下進行加熱，以批次式或連續式方式將芳香族烴蒸發除 去，再將溶劑置換成水溶性有機溶劑，而形成二苯醚^聚 物之水溶性有機溶劑溶液。此時加熱中之加熱媒體溫度， 為了抑制由於熱分解而造成的二苯醚低聚物分子量下 降，以低於180°C之溫度為佳，以低於160°C之溫度為更 佳。又’右加熱媒體的溫度為9 0 °C以下，則蒸發效率低， 並不實用。因此，較佳為90°C以上160°C以下。根據以上 理由，較佳地選擇於減壓下進行蒸發除去操作。 溶劑置換後二苯醚低聚物水溶性有機溶劑溶液中之芳 香族烴殘渣，因於後述使用水進行粒子化時會使二苯鰱低 312XP/發明說明書(補件)/96-09/96118689 16 200804460 物成為σ卩刀、’谷著的黏稍物，故以少為佳。具體而士 相對於二苯醚低聚物為5重量%以下，較佳為2 ;、’ 下’更佳為1重量％以下。又，於蒸發除去芳香族。从 可=將氧化聚合中所使用胺類之大半除去。^’ _:藉由將進行分散的水除去，而將本發明之溶劑 士 ::回收的芳香族烴溶劑與氧化聚合中使用的胺： 核：口：液ί利用於聚合。可將餾出液加以靜置，而分 了縮#時間’可使用連續式或批次式離心分 ’之纹分離裝置、或聚結器等過濾器型液液分離裝置 的處理溫度，若為芳香族經的彿點以下==時 下進行分離^ ί香㈣的溶解度變小之咐以 ，仃刀離為k，更佳為代以上、啊以下。 而而/使'合劑置換後的二苯趟低聚物溶液與水接觸， 二：，聚物以粒子狀態析出之粒子化步驟：: 投入_水二 將二苯醚低聚物溶液單獨 二:同投入固形化容器，於預先加入固形化容 :中之水或者水溶性有機溶劑與水的混合溶液中，以 液於固形化容器内進行攪拌而粒子化之:-二二 溶性有機溶劑量，相掛 等此日守之水 20 so ^ 、； 7，、水溶性有機溶劑的總量，較 仫為20〜80重量％之範圍，更佳 里孕乂 溶劑大於該範圍，則即使於固形化容哭〜内均量^若有機 亦無法順利進行，從而發生容^ =混己粒子化 降，故欠佳。X，若有機溶劑小於^后門或者固體收率下 於5亥耗圍，則需使用大量 312XP/發明說明書(補件)/96侧61麵9 17 200804460 $水，而且所得粒子的粒子徑變得小於合適範圍，故欠 佳。對於粒子化中所使用水之導電度，因離子性雜質越少 越好，故必須使用導電度為2mS/m以下的離子交換水。係 -使用較佳為lms/m以下更佳為〇 5mS/m以下的離子交換 • ^。虽使用導電度高的離子交換水時，會產生二苯鱗低聚 物粒子中殘存的離子性雜f增加之問題，故欠佳。 本操作，可以批次式或連續式中之任-；T式進行，盘水 的接觸時間必須至少為30秒以上，較佳為6〇秒以上。因 長時間接觸中由於攪拌翼而導致二苯醚低聚物粒子的粉 坪乂以將於連續式固形化槽中的滞留時間設為j小時以 ^為最it *進行批次式粒子化時存在滯留時間長之特 徵’但以將實施擾拌的時間控制於6小時以内為佳。對於 授拌方法以及授拌翼形狀並無特別限定，但必須將投入的 二苯_低聚物溶液以及經粒子化的二苯醚低聚物粒子於 固形化容器内均勻地循環而使其混合。若循環不充分，則 =杈入的一苯醚低聚物溶液，於在固形化容器内分散之 前’會附著於容器底部或攪拌翼上，並在 起 子化。，因此產生容器内積垢之問題。粒子化之溫度H 〜90C ’較佳為30〜7〇。〇。此處所得二苯越低聚物粒子 之粒子徑，可藉由擾摔翼形狀、㈣動力以及_時間來 才工制，但平均汁，較佳為1〇〜1〇〇〇以爪之粒子徑， 10〜500 em，此就處理二苯醚低聚物粒子而言為佳。 醚低聚物粒子，因係以分散於液體中的聚料溶液形式 得，故繼而利用固液分離將二苯醚低聚物粒子與溶液加^ 312XP/發明說明書(補件)/96·〇9/96118689 18 200804460 對㈣液分離方法並無特別限定，可 =固體與㈣分離之過遽方式、或者利㈣心力: 分離方式。 ^經雜㈣之二料低聚物粒子，繼而制清洗將 ^ 所含的水溶性有機溶劑殘澄等雜質除去。清洗方 :’可舉出：使清洗液連續通過經分離的粒子之清洗方法 (:中洗清洗）、或者將經暫時分離的粒子與清洗液混合並再 :人進行固液分離之方法(再漿化(resiurry)清洗)單獨進 行或者組合後進行丨次或重複進行2次以上之方法。清洗 液’可單獨使用水’或者使用將自甲醇、乙醇、丙醇、丁 醇中選擇的水溶性醇類與水以任意比例混合之醇水溶 液。即使單獨使用水亦可除去水溶性有機溶劑殘潰等雜 質’更佳的是’藉由在清洗液中使用醇水溶液而提高清洗 效率，故為較佳。對於醇的種類，可使用上述任一種，並 無限制，但就工業製造之觀點而言，以廉價的甲醇為佳。 醇水溶液之濃度，以具有以下溶解度之組成為佳。以將對 於二莩醚低聚物清洗液的溶解度設為5g/100g清洗液以 下之組合為佳，更佳的是，以成為2g/100g清洗液以下之 組合為佳。當使用曱醇時，較佳為1〇重量％以上9〇重量％ 以下，更佳為20重量％以上60重量％以下。當具有5g/1〇〇g 清洗液以上的溶解度時，溶解於清洗液中的或者流出的二 苯鱗低聚物量增加，導致收率下降。 殘存的水溶性有機溶劑量，相對於析出的二笨醚低聚物 粒子為10重量％以下，較佳為5%重量以下，更佳為i重 312XP/發明說明書(補件)/9f〇9/96118689 19 200804460 ^以下。對於所使用的清洗液量，若使水溶性有機 殘渣= 交佳範圍内則無特別限制，為二苯 之 10〜10。倍。當水溶性有機溶劑殘量為 ： :;洗:!=效’當小…量%時以再裝化： :乾圍。又’藉由固液分離操作，而將觸媒殘渣 及聚合副產物與水溶性有機溶劑一同除去。對於清洗中戶^ ΪΓΓ二電度’因離子性雜質越少越好，故必須使用導 電度為2ms/m以下的離子交換水。使用The above-exemplified method for separating from a chelating agent is selected. The contact temperature and the separation temperature with water are not particularly limited, but can be effectively shortened by 4 (rc or more, preferably 80 ° C or higher). The cleaning is carried out by repeating the water twice or more times. The cleaning with water is carried out until the catalyst metal residue in the polymerization reaction solution of the diphenyl ether oligomer is 1 gg/g or less, preferably 5 〇#g/g, relative to the diphenyl ether oligomer. The following is more preferably ΙΟ/zg/g or less. Further, the conductivity of the water after the final washing is preferably 50 mS/m or less, more preferably 2 〇 mS/m or less. When it is plural times, one or all of the water used for the nth time may be recycled during the (n-1)th water washing. Further, the water after the i-th water washing may be part of the water washing number. Or all used to adjust the aqueous solution of the chelating agent used in the polymerization stop. Thereby, the present invention; the diphenyl ether oligomer solution used. Next, the aromatic solution of the diphenyl scale oligomer solution of the present invention is obtained. After the family smoke is replaced by a water-soluble organic solvent having a higher boiling point than the aromatic hydrocarbon, the second group is oligomerized The method is carried out by contacting the solution with water to form the diphenyl ether oligomer in the form of the particles 2. In the method for producing PPE, the method of obtaining the PPE particles by directly reacting with the alcohol is carried out. - General formula I / due to the low molecular weight of diphenyl ether oligomers, so the mixture of aromatic hydrocarbons and alcohols: 312XP / invention manual (supplement) / 96_09 / 9618689 15 200804460 agent shows solubility. + contact The presence of the following deficiency benzene yoke oligomer solution is directly lower than the alcohol rate, and it is produced, and the dissolution is not clear. The 铒 ,, knife / 耆 耆 黏 而 难以 难以 难以 难以 难以 难以 固体 固体 固体 固体 固体 固体 固体 固体Aromatic hair 4::4, the aromatic solvent of the polymer solution, the second squamous oligomer II:: 接 = 吏 organic solvent 'and after the replacement # can approve the night / water contact to make the diphenyl ether low The polymer is a method of solving the above problems of oligomerization with diphenyl ether by the method of particle core. The water-soluble organic solvent used in the replacement of ☆ back i is higher in boiling point than in the reaction solvent (4) An aromatic hydrocarbon solvent. Specifically, dimethyl decylamine, N,N-dimethylacetamide or |N-methyl It is preferred to use a ketone or a bis sulfoxide, and it is more preferable to use N,N-dimethyl hydrazine in terms of ease of handling. The solvent is replaced by a diphenyl ether oligomer solution and water-soluble in advance. The organic solvent is mixed or separately introduced into a distillation apparatus, heated under atmospheric pressure or reduced pressure, and the aromatic hydrocarbon is evaporated and removed in a batch or continuous manner, and then the solvent is replaced with a water-soluble organic solvent to form a diphenyl ether. a water-soluble organic solvent solution of the polymer. At this time, the temperature of the heating medium in the heating, in order to suppress the molecular weight drop of the diphenyl ether oligomer due to thermal decomposition, preferably lower than 180 ° C, preferably less than 160 The temperature at °C is better. Moreover, the temperature of the right heating medium is below 90 °C, and the evaporation efficiency is low, which is not practical. Therefore, it is preferably 90 ° C or more and 160 ° C or less. For the above reasons, it is preferred to carry out the evaporation removal operation under reduced pressure. After the solvent replacement, the aromatic hydrocarbon residue in the diphenyl ether oligomer water-soluble organic solvent solution will cause the diphenyl hydrazine low 312XP/inventive manual (supplement)/96-09/96118689 due to the use of water for particle formation as described later. 16 200804460 The object becomes a σ 卩 knife, 'the sticky thing of the valley, so it is better. The specific amount is 5% by weight or less, preferably 2%, more preferably 1% by weight or less based on the diphenyl ether oligomer. Further, the aromatics were removed by evaporation. It is possible to remove most of the amines used in the oxidative polymerization. ^' _: The solvent used in the solvent of the present invention and the amine used in the oxidative polymerization are used to remove the water to be dispersed, and the core: port: liquid is used for the polymerization. The distillate can be allowed to stand still, and the treatment time of the filter type liquid-liquid separation device such as the continuous or batch type centrifugal separation device or the coalescer can be used if the time is reduced. The aromatic point of the Buddha's point is ============================================================================== And / / the mixture of the diphenyl sulfonium oligomer solution after contact with water, two:, the particle precipitation step of the polymer in the particle state:: input _ water two diphenyl ether oligomer solution alone two: The same is added to the solidification container, and is added to the solid solution: water or a mixed solution of a water-soluble organic solvent and water in advance, and the liquid is stirred in the solidification container to be granulated: - the amount of the di-soluble organic solvent, Between the water and the water 20 so ^, 7, 7, the total amount of water-soluble organic solvent, which is in the range of 20 to 80% by weight, and the better the solvent is larger than the range, even in the solid content Crying ~ internal average ^ If the organic can not be carried out smoothly, so the occurrence of ^ ^ mixed particles, so it is not good. X. If the organic solvent is less than the back door or the solid yield is less than 5 Hz, a large amount of 312XP/invention specification (supplement)/96 side 61 surface 9 17 200804460 $ water is used, and the particle diameter of the obtained particles is changed. It is less than the proper range, so it is not good. The conductivity of water used in the particle formation is preferably as small as possible because of ionic impurities. Therefore, it is necessary to use ion-exchanged water having a conductivity of 2 mS/m or less. - Use ion exchange that is preferably lms/m or less, more preferably 〇 5mS/m or less. When ion-exchanged water having high conductivity is used, there is a problem in that the ionic impurity f remaining in the diphenyl squamous oligomer particles is increased, which is not preferable. This operation can be carried out in any of batch or continuous mode; the T-type, the contact time of the tray water must be at least 30 seconds, preferably more than 6 seconds. When the residence time of the diphenyl ether oligomer particles due to the stirring wings in a long-term contact is set to j hours in the continuous solidification tank, the batch is used for the batching of the particles. There is a characteristic that the residence time is long', but it is preferable to control the time for carrying out the scramble to be within 6 hours. The method of the mixing method and the shape of the mixing wing are not particularly limited, but it is necessary to uniformly circulate and mix the charged diphenyl-oligomer solution and the particle-formed diphenyl ether oligomer particles in the solidification container. . If the cycle is insufficient, the solution of the insoluble phenylene ether oligomer will adhere to the bottom of the vessel or the agitating wing before being dispersed in the solidification vessel and will be activated. Therefore, there is a problem of scale buildup in the container. The temperature of the particle formation H to 90C ' is preferably 30 to 7 Å. Hey. The particle diameter of the diphenyl oligomer particles obtained here can be produced by the shape of the wobble wing, (4) power and time, but the average juice is preferably 1〇~1〇〇〇. The diameter is 10 to 500 em, which is preferable for treating the diphenyl ether oligomer particles. The ether oligomer particles are obtained in the form of a polymer solution dispersed in a liquid, and then the diphenyl ether oligomer particles and the solution are added by solid-liquid separation. 312XP/Invention Manual (Supplement)/96·〇 9/96118689 18 200804460 There is no particular limitation on the (IV) liquid separation method, which can be = solid and (4) separation method, or (4) heart force: separation method. ^ After the impurity particles of the second (four), the impurities are removed by removing the impurities such as the water-soluble organic solvent contained in the cleaning. Cleaning side: 'It can be mentioned: a cleaning method in which the cleaning liquid is continuously passed through the separated particles (: washing in the middle), or a method in which the temporarily separated particles are mixed with the cleaning liquid and again: a method of solid-liquid separation by a person (again Slurry cleaning) A method in which the treatment is carried out separately or in combination, or repeated twice or more. The cleaning liquid 'can be used alone' or an aqueous alcohol solution in which a water-soluble alcohol selected from methanol, ethanol, propanol or butanol is mixed with water in an arbitrary ratio is used. Even if water is used alone, impurities such as water-soluble organic solvent residue can be removed. More preferably, it is preferable to use an aqueous alcohol solution in the cleaning liquid to improve the cleaning efficiency. As the kind of the alcohol, any of the above may be used without limitation, but from the viewpoint of industrial production, it is preferred to use inexpensive methanol. The concentration of the aqueous alcohol solution is preferably a composition having the following solubility. The solubility in the diterpene ether oligomer cleaning solution is preferably 5 g/100 g or less, more preferably 2 g/100 g of the cleaning liquid or less. When decyl alcohol is used, it is preferably from 1% by weight to 9% by weight, more preferably from 20% by weight to 60% by weight. When having a solubility of 5 g/1 〇〇g or more of the cleaning liquid, the amount of the diphenyl squamous oligomer dissolved in the cleaning liquid or flowing out is increased, resulting in a decrease in yield. The amount of the water-soluble organic solvent remaining is 10% by weight or less, preferably 5% by weight or less, more preferably i weight 312XP/invention specification (supplement)/9f〇9 with respect to the precipitated dimer ether oligomer particles. /96118689 19 200804460^The following. The amount of the cleaning liquid to be used is not particularly limited as long as the water-soluble organic residue is within a good range, and is 10 to 10 of diphenyl. Times. When the residual amount of the water-soluble organic solvent is: :; Wash: ! = Effect ' When the amount is small... Repacking: : Dry circumference. Further, the catalyst residue and the polymerization by-product are removed together with the water-soluble organic solvent by a solid-liquid separation operation. For cleaning, the amount of ionic impurities is as small as possible. Therefore, it is necessary to use ion-exchanged water having a conductivity of 2 ms/m or less. use
=以下更輪5ms/in以下的離子交換水。當使用J IS:::::換水時’會產生殘存於二苯醚低聚物粒子 上的離子性雜質增加之問題，故欠佳。又，可 設為，，並將第n次使用的清洗液的一部分：者：部 作為f(n-l)次清洗液而加以循環使用。可藉由以上作 而以高收率獲得二苯醚低聚物粒子。 木 =隨分離中所排“㈣成分以及清洗所得 2洗液加以蒸館’取出醇、水及水溶性有機溶劑，㈣ 為回收办劑而使用於後面的聚合、粒子化及 中。於回收基|留步驟由 _ _ 丁 /月况 U 中可將於111液分離中排出的水溶性 =機溶劑與水、及將作為清洗液而排出的醇與水預先、、9入 =者=導入蒸難置’於常壓或減壓下加熱，以批：； 進：分鶴。對於蒸館，若採用實用條件則無限制，二： “沸點的水溶性有機溶劑時，為了提高效率則以減= 顧為佳。當清洗液為甲醇水溶㈣，繼_之後可進行S 312ΧΡ/發明說明書(補件)/96-09/96118689 200804460 制’則可加以回收再利用。;二:：對^進行濃度控 中，再次使用於回收步驟。““ 5人後面的蒸館液 對於清洗後獲得之二苯 埶（乾燁^低水物粒子的濾餅，可將其加 二。\其溶解”水溶性芳香族煙中而進行脫 合氣體環境中進扞。1 士 、 “、μ r玍乱體的犯 丨捽。# 、 /、中，以於氮氣環境氣體中進行為 二：：士 Γ40〜16rc之溫度範圍為佳。當溫度範圍低 會溶融，故欠佳。乾燥，係藉由常Μτ之氣錢 、木^於1〜700T〇rr範圍内之減壓乾燥等習知方法， =次式或連續式方式進行。乾燥中，較佳的是，乾燥至 〜存於二苯ϋ低聚物粒子中的揮發成分為5%以下、較佳 為U以下。將揮發成分量定義為·於真空乾燥機中進行 120 c 24小吋（真空計）真空乾燥後之重量減少量。再者， =¾，分之主成分為水及水溶性有機溶劑殘渣。使用非水 各性^香族烴之脫水，係以二苯醚低聚物濃度成為1〇〜 6〇重1 %之方式將二苯醚低聚物溶解於非水溶性芳香族烴 中，並將經分離的水進行液液分離及/或於常壓或減壓下 將二苯醚低聚物溶液加熱而將水蒸發除去。 本叙明中所得二苯醚低聚物，可單獨使用，或者將分子 量不同的二苯醚低聚物以任意比例混合後使用，或者將其 與原料二元酚化合物以任意比例混合後使用。本發明中所 312XP/發明說明書(補件)/96-09/96118689 21 200804460 得二苯㈣聚物，可以原來的形態使用或者將其溶解於溶 劑中使用’進*可將富含反應性的QH基加峰飾後使 用。對於該0H基之修飾反應並無特別限定，例如可例示： 與環氧氯丙烧反應而將0H基修飾成縮水甘油基之方法， 與氯曱基苯乙烯反應而將0H基修飾成甲基苯乙烯基之方= The following rounds of ion exchange water below 5ms/in. When JIS::::: is used for water replacement, the problem of an increase in ionic impurities remaining on the diphenyl ether oligomer particles is unfavorable. Further, it is possible to recycle a part of the cleaning liquid used for the nth time as a f(n-1) cleaning liquid. The diphenyl ether oligomer particles can be obtained in high yield by the above. Wood = with the "(4) ingredients in the separation and the 2 washes obtained by washing, steaming the house to remove the alcohol, water and water-soluble organic solvent, (4) for the recovery agent and used in the subsequent polymerization, particleization and medium. The leaving step is _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Difficult to 'heat under normal pressure or reduced pressure, to batch:; Into: split crane. For steaming hall, if using practical conditions, there is no limit, two: "When boiling point of water-soluble organic solvent, in order to improve efficiency, reduce = Gu Weijia. When the cleaning solution is methanol-soluble (4), the S 312 ΧΡ / invention manual (supplement) / 96-09/96118689 200804460 can be recycled and reused. ; 2:: Concentration control of ^, used again in the recovery step. “The steaming liquid behind the 5 people will be degassed for the diphenyl hydrazine obtained after washing (dry 烨^ filter cake of low water particles, which can be added to the water-soluble aromatic smoke) In the environment, 1 士, ", μ r 玍 玍 丨捽 丨捽 # # # # # # # # # # # # # # # # # # 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气 氮气It is low in melting, so it is not good. Drying is carried out by a conventional method such as vacuuming in the range of 1 to 700 T rr, in the range of 1 to 700 T rr, in a secondary or continuous manner. Preferably, the volatile component to be dried in the diphenylhydrazine oligomer particles is 5% or less, preferably U or less. The amount of the volatile component is defined as: 120 c 24 hours in a vacuum dryer. (vacuum gauge) The weight reduction after vacuum drying. In addition, =3⁄4, the main component is water and water-soluble organic solvent residue. Dehydration of non-aqueous various aromatic hydrocarbons is used, and diphenyl ether is oligomerized. Dissolving the diphenyl ether oligomer in the water-insoluble aromatic hydrocarbon in such a manner that the concentration of the substance is 1 〇 to 6 〇 and 1% by weight The separated water is subjected to liquid-liquid separation and/or the diphenyl ether oligomer solution is heated under normal pressure or reduced pressure to evaporate the water. The diphenyl ether oligomer obtained in the present invention can be used alone. Alternatively, the diphenyl ether oligomers having different molecular weights may be used in an arbitrary ratio, or may be used after being mixed with the raw material dihydric phenol compound in an arbitrary ratio. In the present invention, the 312XP/invention specification (supplement)/96-09 /96118689 21 200804460 Derived diphenyl (tetra) polymer, which can be used in its original form or dissolved in a solvent. It can be used after adding the reactive QH group to the peak. For the modification of the 0H group There is no particular limitation, and for example, a method of modifying a 0H group to a glycidyl group by reacting with epichlorohydrin, and reacting with a chlorostyrene styrene to modify a 0H group to a methylstyryl group can be exemplified.
^，與均苯四甲酸、偏苯酸或料生物反應而將〇H :4飾成馱酐基之方法’與氯化氰反應而將⑽基修飾成 氰酸酯基之方法等。 籲（實施例） 、下土於δ成例貝知例及比較例來具體說明本發明， 但本發明並不特別限定於以下實施例。所使用的藥品中， t2，3,3’’5,5、六甲基-(1，Γ-聯苯二醇之純度 ^ 98%，’ 雜質為 2,2，’3,3，，5,5，一 六甲基，一聯 Γ入I4 _二醇上結合有1分子以上的2, 3, 6_二甲基酚之 ::物。2, 6-二甲基龄之純度為99%，雜質為甲基紛及： 甲基酚。 — ，低聚物之聚合收率，係根據取出的甲苯溶 口溶液中的真空乾燥樣品重量而求出二苯醚低聚物回 里’再以與對應於加入單體類的理論收量之比而求出。 ::化後之收率，係根據加…，N—二甲基乙醢胺溶 ，文It她聚物濃度及粒子化乾燥後的重量而求出。 對於为子量，係利用GPC，根據標 :’作為聚苯乙稀換算分子量而求出數量平均:二;出： 體的測定裝置，係使用島津製作所股份有限公司製咖系、 312XP/發明說明書(補件)/96〇9/961〗86紗 ^ 200804460 統，GPC 管柱係使用 Shodex 製 GPCKF-801、GPCKF-802、 GPCKF-803、GPCKF-804，於40°C的THF溶液中利用示差 折射計檢測器進行测定。 (合成例1) 於氮氣環境氣體中，於附有攪拌裝置、溫度計、檔板、 氣體導入管、排出氣體冷卻管、排出氣體氧氣濃度測定裝 置之SUS316C—部分為SUS304)製200L附夾套聚合釜内， 加入 4089g 之 2, 2’，3, 3’，5, 5’ -六曱-(1，Γ -聯苯）-4,4’-⑩二醇、7390g之2, 6-二曱基酚、89kg之曱苯、47kg之曱 醇、625g之N-丁基二甲胺、60g之N，Ν’ -二-第三丁基乙 二胺、51g之溴化亞銅。開始攪拌，將溫水於夾套中流動 將聚合爸内控制於40°C。待溫度穩定時，以8.5 Nm3/hr 吹入以氮氣稀釋成氧氣濃度為8%的空氣，開始聚合。聚 合開始230分鐘後，因排出氣體的氧氣濃度開始上升 0. 5%，故停止導入稀釋空氣。投入47kg乙二胺四乙酸鈉 _水溶液（内有38Og乙二胺四乙酸鈉）以終止聚合。將有機 相與水相於聚合爸内靜置分離並除去水相，再次投入45kg 離子交換水與有機相攪拌混合，然後進行靜置分離而將有 機相與水相分離。重複進行2次該水清洗操作，而獲得二 苯醚低聚物之11 · 1重量％曱苯溶液。（以蒸發器將一部分 曱苯溶液濃縮乾燥，進而於箱形真空乾燥機内進行120°C /48小時（真空計）真空乾燥，結果為聚合收率為98%，數 量平均分子量為989。） (合成例2 ) 312XP/發明說明書(補件)/96-09/96118689 23 200804460 於合成例1中，除於聚合釜内加入9〇9g之 2, 2’，3, 3’，5, 5’ -六 f 基-(1，Γ —聯苯）乂 4, _二醇、ι〇264 2之2, 6-二甲基齡以外’其餘以與合成们㈣之方式進 行，而獲得二苯醚低聚物之10.8重量％甲苯溶液。（以盥 合成例1同樣之方式將其-部分進行乾燥，結果為聚合收 率為97%’數量平均分子量為3421。） (實施例1) 於lOOOg之合成例1中所得二苯醚低聚物的甲苯溶液中 加入450g之N，N-二曱基乙醯胺（以下稱為dmac)，以塔徑 25mm、理論塔板數15段（上段7板，下段8板）、釜溫度（熱 媒溫度）115t、塔頂減壓度10Torr之條件進行連續蒸 餾，而獲得二苯醚低聚物之N，N—二甲基乙醯胺溶液。以6 小時之平均計，進料量為l99g/hr、底部取出量為77 g/hr、回流比為〇· 24、爸内滯留時間為5· 〇小時。二苯 醚低聚物濃度為20· 8重量％，曱苯殘量相對於二苯醚低聚 物為0 · 9重量％。自蒸餾塔的塔頂侧獲得產生白色渾濁之 餾出液。將餾出液靜置分離，而獲得曱苯99· 3重量％、^— 丁基二甲胺0· 7重量％、水0.04重量％之混合溶液。曱苯 之回收率為98. 5%，N-丁基二曱胺之回收率為98. 5%。繼 而，一面攪拌一面向加入有400g離子交換水的往復攪拌 式固形化槽中投入400g二苯醚低聚物的n，N -二曱基乙醯 胺溶液並進行粒子化，可在固形化槽内無固體附著的情況 下獲得二苯醚低聚物粒子之漿料。將所得二苯醚低聚物粒 子過濾’以10 0 0 g之3 0重量％曱醇水溶液進行清洗，於真 312XP/發明說明書(補件)/96·〇9/96118689 24 200804460 空乾燥機中進行12(TC、24小時乾燥。 粒子之收率為96%，數量平均分旦、侍二苯醚低聚物 ^ J刀于里為1020。 將及固液分離的液體成分與清洗所 ^ 出液加以混合，以塔徑25職、理认&叙、甲醇水排 ^ η, β/ί〇^ 板數21.3、塔頂、;田 度63〜64 C、塔頂大氣壓之條件進行批 。頁/皿 回收率獲得98重量％以上之甲醇。繼 ，而以91% 丁鮮 《而以挞頂、、西硌〇 〇 ’C、塔頂減壓度150_之條件繼。二二： /水/DMAC餾去，然後以塔頂溫度91〜將甲醇 70torr之條件，以84%回收率獲得99重量〔頁度 有機溶劑的二曱基乙醯胺。 ° 之7 >谷性 (實施例2) 於實施例1中，除使用於合成例2中 之甲苯溶液以外，其餘以與實施例 作，而獲得二苯醚低聚物之N，N一二甲基乙醯胺溶液。以、 小時之平均計，進料量為203g/hr、底部取出量為79 g/hr、回流比為〇· 24、蚤内滯留時間為4· 8小時。二苯 鍵低聚物濃度為19. 7重量％，甲苯殘量相對於二苯喊= 物為0.5重量％。自蒸餾塔的塔頂侧獲得產生白色混濁之 餾出液。將餾出液進行靜置分離，而獲得甲苯99 3重旦 %、.丁基二甲胺0.7重量％、水〇.〇3重量％之混合溶液= 甲苯之回收率為98. 7% ’ N- 丁基二甲胺之回收率為 98·7%。繼而，以與實施例〗同樣之方式進行粒子化，而 獲得二苯醚低聚物粒子。固形化槽内無固體附著。除於琴 得粒子的清洗液中使用50重量％曱醇水溶液以外，其餘以 312ΧΡ/發明說明書(補件)/96-09/96118689 25 200804460 。收率為98%，數 與實施例i同樣之方式進行清洗及乾燥 量平均分子量為3440。 將經固液分離的液體成分與清洗所得粒子的甲醇水排 =力於塔徑25mm、理論塔板數μ、塔頂溫 =二壓之條件進行批次蒸館，而以㈣ :=二Γ，°以上之甲醇。繼而以塔頂溫度28〜 、合頂賴度15i)t°rr之條件繼續進行基顧，顧去甲 醉/水/:#然後以塔頂溫度91〜9代、塔頂減麼度 m町之條件，α85%回收率獲得99^量％以上之水溶性 有機溶劑的二甲基乙醯胺。 (實施例3) 於貫施例1中，除將蒼溫度（熱媒溫度）設為、將 塔頂減壓度設為60Torr以外，其餘以與實施例i同樣之 方式進行連續蒸餾，而獲得二苯醚低聚物之n，n—二曱基 乙醯胺溶液。以6小時之平均計，進料量為2〇6g/hr、^ φ部取出量為80g/hr、回流比為〇·35、釜内滯留時間為4 9 小時。二苯醚低聚物濃度為丨9· 9重量％，甲苯殘量相對於 一笨醚低聚物為1 · 1重量％。繼而，以與實施例1同樣之 方式進行操作，而獲得二苯醚低聚物粒子。固形化槽内無 ‘固體附著，收率為98%，數量平均分子量為ι〇〇2。 _ (實施例4) 於實施例1中，除將蚤溫度設為l60°c、將塔頂減壓度 設為200Torr以外，其餘以與實施例1同樣之方式進行連 續蒸餾，而獲得二苯醚低聚物之N，N-二曱基乙醯胺溶液。 312XP/發明說明書(補件)/96-09/96118689 26 200804460 以6小時之平均計，進料量為200g/hr，底部取出量為乃 g/hr，回流比為〇.52，釜内滯留時間為4 7小時。二# 喊低聚物濃度為20. 9重量%、曱苯殘量相對於二苯醚低； ‘物為0.4重量％。繼而以與實施例！同樣之方式進行操 ‘而獲得二苯_低聚物粒子。固形化槽内無固體附著，'收 為99%，數量平均分子量為998。 (實施例5) 於實施例1巾’除終溫度設為2G(r(：、將塔頂設 氣壓以外，其餘以與實施例1同樣之方式進行連續基顧， 而獲得二苯鴨物之N，N_二甲基乙醯胺溶液。以、、、 時之平均計，進料量為2〇lg/hr，底部取出量為㈣^， 滯留時間為5.1小時。二苯鍵低聚 。Γ;:°/ :ι “、甲苯殘量相對於二笨醚低聚物為 0.4重篁於繼而’以與實施例i同樣之方式進行操作， =獲得二苯驗低聚物粒子。粒子化槽内 為Θ8%，數量平均分子量為965。 了考彳文旱 (合成例3 ) 二中，除代替甲苯而於聚合爸内加入& 於實施例1中所得之时甲苯溶液、不投人Ν_τ基二甲 胺以外’其餘以與合成例i同樣之方式進 二苯it低聚物之m重量<乍獲件 浐之mi划、 （以與合成例1同 板之方式將其一部分進行乾燥，結果 數量平均分子量為992。） ° (實施例6) 312ΧΡ/發明說明書(補件)/96-09/96118689 27 200804460 於lOOOg合成例3中所得二苯醚低聚物之甲苯溶液中， 加=於實施例1、2中回收的45〇§之N，N—二曱基乙醯胺， 以塔徑25mm、理論塔板數15(上段7、下段8)、荃溫度（熱 媒溫度M15T：、塔頂減壓度胸rr之條件進行連續蒸 餾’而獲得二苯it低聚物之N，[二甲基乙酿胺溶液。 時之平均進料量為200g/hr ’底部取出量為78g/hr，回流 比為0.24,釜内滯留時間為5. 〇小時。二苯醚低聚物^ ^為20. 4重量％’甲苯殘量相對於二苯喊低聚物為〇 7重 量％。自蒸餾塔的塔頂側獲得產生白色混濁之餾出液。將 其靜置分離，而獲得曱苯99 2重量％、N一丁基二甲胺〇 7 重量％、水0.05重量％之混合溶液。甲苯之回收率為 98.6%，N-丁基二甲胺之回收率為98 6%。繼而，一面攪 掉-面向加入有400g離子交換水的往復授摔式固形化槽 :投入400g二苯醚低聚物的N，N_:甲基乙醯胺溶液並‘ 行粒子化，可在固形化槽内無固體附著的情況下庐得二 醚低聚物粒子之聚料。將所得二苯醚低聚物粒^^彳^過 ，，使用於實施例1、2中回收的甲醇，以1〇〇〇g之3〇重 量％甲醇水溶液進行清洗，於真空乾燥機中進行 24小時乾燥，得二苯㈣聚物粒子之收率為㈣，數二 平均分子量為1005。 里 將經固液分離的液體成分與清洗所得粒子的甲醇水 出液加以混合，以塔徑25则1、理論塔板數21 3、挞音θ 度63〜6代、塔頂為大氣壓壓力之條件進行批次“二 而以92%回收率獲得98重量％以上之甲酶。 ，吁繼而，以塔頂 312ΧΡ/發明說明書(補件)/96-09/96118689 28 200804460 溫度28〜6Gt：、塔頂減壓度㈣町之條件繼續進行蒸 餾，餾去曱醇/水/DMAC後，以塔頂溫度91〜93t：、拔頂 減壓度7〇torr之條件，以85%回收率獲得99重量％二上 之水溶性有機溶劑的二曱基乙醯胺。 (比較例1) 一=攪拌一面將200g於合成例i中所得二苯醚低聚物 的曱苯洛液投人加人有4陶粒子化溶劑之往復攪掉式固 形化枱中，進行粒子化。粒子化溶劑係使用甲醇、乙醇、 泰2丙醇。即使使用其中任—粒子化溶劑，二苯醚低聚物均 變為有一部分產生溶著的黏拥物，而黏附於攪拌翼及固形 化槽壁上。一面以粒子化溶劑將固形化槽内加以清洗，一 面回收二苯醚低聚物粒子。收率為78%，數量平均分子量 為1237，低分子量體溶解於粒子化溶劑中，溶出並有損 失。 、 (比較例2) •於比較例1中’除使用於合成例2中所得二苯醚低聚物 的曱苯溶液以外，其餘藉由與比較例1同樣之方法進行粒 子化。即使使用任一粒子化溶劑，均有一部分二苯醚低聚 物成為溶著的黏稠物，而黏附於攪拌翼及固形化槽壁上。 一面以粒子化溶劑將固形化槽内加以清洗，一面回收二苯 醚低聚物粒子。收率為81%，數量平均分子量為3848,低 分子量體溶解於粒子化溶劑中，溶出並有損失。 (比較例3) ' 於氮氣環境氣體中，向附有攪拌裝置、溫度計、檔板、 312XP/發明說明書(補件)/96-09/96118689 29 200804460 氣體導入管、排出氣體冷卻管、排出氣體氧氣濃度测定裝 置之SUS316C —部分為SUS304)製200L之附夾套聚合蚤 内，添加7390 g之2, 6-二甲基酴、89kg之曱苯、47kg 之曱醇、625g之N-丁基二曱胺、60g之Ν，Ν’ -二-第三丁 基乙二胺、51g溴化亞銅。開始攪拌，將溫水在夾套中流 Μ 動並將聚合釜内控制於40°C。待溫度穩定時，開始以8. 5 Nm3/hr吹入以氮氣將氧氣濃度稀釋成8%的空氣，開始聚 合。聚合開始225分鐘後，因排出氣體的氧氣濃度開始上 •升1. 0%，故停止導入稀釋空氣，並投入47kg乙二胺四乙 酸鈉水溶液（内有380g乙二胺四乙酸鈉）以終止聚合。將 有機相與水相於聚合爸内進行靜置分離並除去水相，再次 投入45kg離子交換水與有機相攪拌混合，然後進行靜置 分離而將有機相與水相分離。重複2次該水清洗操作，而 獲得聚二苯醚之7.6重量％曱苯溶液。（以蒸發器將一部分 曱苯溶液進行濃縮乾燥，進而於箱形真空乾燥機内進行 120°C/48小時（真空計）真空乾燥，結果為聚合收率為 * 99%，數量平均分子量為14000。） 於1000g之所得聚二苯醚的曱苯溶液中加入310g之 N，N-二曱基乙醯胺，發現溶液懸濁化並有一部分黏稠物析 . 出。進而，欲直接將其進料於塔徑25mm、理論塔板數15 (上 段7、下段8)之蒸餾設備中，但泵停止，無法進行溶劑置 換。因此，將該懸濁化的甲苯-二甲基乙醯胺溶液的一部 分置於茄形燒瓶中，於蒸發器中簡易地進行溶劑置換，但 與曱苯餾出的同時成為黏度更高之懸濁液，無法將其取 312XP/發明說明書(補件)/96-09/96118689 30 200804460 出ΟA method of reacting quinone H:4 with a phthalic anhydride group by reacting with pyromellitic acid, a meta-benzoic acid or a material to react with cyanogen chloride to modify a (10) group into a cyanate group. The present invention is specifically described in the following examples, and the present invention is not limited to the following examples. Among the drugs used, t2,3,3''5,5, hexamethyl-(1, Γ-biphenyl diol purity ^ 98%, 'impurities are 2, 2, '3, 3, 5 , 5, hexamethyl, a combination of 1 and 2,3,6-dimethylphenol in the I4-diol coupled with: 2, 6-dimethyl-methyl purity of 99 %, the impurity is a methyl group: methylphenol. - , the polymerization yield of the oligomer, based on the weight of the vacuum dried sample in the extracted toluene solution to determine the diphenyl ether oligomer back It is determined by the ratio with the theoretical yield corresponding to the added monomer. The yield after the addition is based on the addition of N-dimethylacetamide, the concentration of it and its particle formation. It is determined by the weight after drying. For the sub-quantity, GPC is used to obtain the number average according to the standard: 'The molecular weight is converted from polystyrene: two; and the measurement device for the body is Shimadzu Corporation. Department of coffee, 312XP / invention manual (supplement) / 96〇9/961〗 86 yarn ^ 200804460 system, GPC pipe column using Shodex GPCKF-801, GPCKF-802, GPCKF-803, GPCKF-804, at 40 °C in THF solution The measurement was carried out by a differential refractometer detector. (Synthesis Example 1) In a nitrogen atmosphere, a SUS316C with a stirring device, a thermometer, a baffle, a gas introduction pipe, an exhaust gas cooling pipe, and an exhaust gas oxygen concentration measuring device was used. SUS304) 200L jacketed polymerization reactor, adding 4089g of 2, 2', 3, 3', 5, 5'-hexafluoro-(1, fluorene-biphenyl)-4,4'-10 diol, 7390g of 2,6-dinonylphenol, 89kg of terpene, 47kg of sterol, 625g of N-butyl dimethylamine, 60g of N, Ν'-di-t-butylethylenediamine, 51g Cuprous bromide. Stirring was started, and warm water was flowed through the jacket. The polymerization dad was controlled at 40 °C. When the temperature was stable, air was diluted at 8.5 Nm3/hr and diluted with nitrogen to an oxygen concentration of 8% to start polymerization. After 230 minutes from the start of polymerization, the concentration of oxygen in the exhaust gas began to rise by 0.5%, so the introduction of dilution air was stopped. 47 kg of sodium edetate aqueous solution (38 Og of sodium edetate) was added to terminate the polymerization. The organic phase and the aqueous phase were allowed to stand in the polymerization dad to separate and remove the aqueous phase, and 45 kg of ion-exchanged water was again introduced and stirred and mixed with the organic phase, followed by standing separation to separate the organic phase from the aqueous phase. This water washing operation was repeated twice to obtain a 11.1% by weight of a benzene solution of the diphenyl ether oligomer. (A part of the benzene solution was concentrated and dried by an evaporator, and vacuum-dried at 120 ° C / 48 hours (vacuum gauge) in a box-shaped vacuum dryer, and the polymerization yield was 98%, and the number average molecular weight was 989.) Synthesis Example 2) 312XP/Invention Manual (Supplement)/96-09/96118689 23 200804460 In Synthesis Example 1, except that 9〇9g of 2, 2', 3, 3', 5, 5' was added to the polymerization vessel. - hexa-f-(1, fluorene-biphenyl) 乂 4, _ diol, ι 264 2 2, 6-dimethyl age other than the remainder and the synthesis (4), to obtain diphenyl ether A 10.8 wt% toluene solution of the oligomer. (The part was dried in the same manner as in the synthesis of Example 1 to give a polymerization yield of 97%. The number average molecular weight was 3421.) (Example 1) Diphenyl ether oligomerization obtained in Synthesis Example 1 of 1000 g 450 g of N,N-dimercaptoacetamide (hereinafter referred to as dmac) was added to the toluene solution of the product, with a column diameter of 25 mm and a theoretical number of plates of 15 (upper plate 7 plates, lower plate 8 plates), kettle temperature (heat) The solvent was subjected to continuous distillation under the conditions of a temperature of 115 t and a column decompression degree of 10 Torr to obtain a N,N-dimethylacetamide solution of a diphenyl ether oligomer. On the average of 6 hours, the feed amount was l99g/hr, the bottom withdrawal amount was 77 g/hr, the reflux ratio was 〇·24, and the dad's residence time was 5·〇 hours. The diphenyl ether oligomer concentration was 20.8 wt%, and the residual parabens was 0. 9 wt% with respect to the diphenyl ether oligomer. A white turbid distillate was obtained from the top side of the distillation column. The distillate was allowed to stand for separation to obtain a mixed solution of toluene 99.3% by weight, ?-butyldimethylamine 0.7% by weight, and water 0.04% by weight. 5%。 The recovery of the benzene is 98.5%, the recovery of N-butyl dimethylamine is 98.5%. Then, while stirring, a solution of n,N-dimercaptoacetamide in which 400 g of a diphenyl ether oligomer is added to a reciprocating stirring solidification tank to which 400 g of ion-exchanged water is added, and granulating, can be used in the solidification tank. A slurry of diphenyl ether oligomer particles was obtained without solid adhesion. The obtained diphenyl ether oligomer particles are filtered and washed with 100% by weight of a 30% by weight aqueous solution of decyl alcohol, in the true 312XP/invention specification (supplement)/96·〇9/96118689 24 200804460 air dryer It was subjected to 12 (TC, 24 hours drying. The yield of the particles was 96%, the number averaged denier, and the diphenyl ether oligomer was 1020. The liquid component separated from the solid and liquid was cleaned. The liquid is mixed and batched under the conditions of column diameter 25, literacy & Syrian, methanol water discharge η, β/ί〇^ plate number 21.3, tower top, field 63~64 C, and tower top atmospheric pressure. The page/dish recovery rate obtained 98% by weight or more of methanol. Subsequently, with 91% Ding Xian, the condition was followed by the dome, Xiqiao 'C, and the top decompression degree 150_. The water/DMAC was distilled off, and then 99 weights were obtained at an 84% recovery rate under the conditions of an overhead temperature of 91 to 70 Torr of methanol (the organic solvent of dimercaptoacetamide. 7 7 > gluten (Example) 2) In Example 1, except for the toluene solution used in Synthesis Example 2, the N, N-dimethylene of the diphenyl ether oligomer was obtained in the same manner as in the examples. The acetamide solution has an average feed hour of 203 g/hr, a bottom withdrawal of 79 g/hr, a reflux ratio of 〇·24, and a residence time of 4.8 hours. The diphenyl bond is low. The concentration of the polymer was 19.7% by weight, and the residual amount of toluene was 0.5% by weight relative to the diphenyl sulfonate. A white turbid distillate was obtained from the top side of the distillation column. The distillate was allowed to stand for separation. The recovery ratio of toluene 99 3 heavy denier %, .butyl dimethylamine 0.7 wt %, water 〇 〇 3 wt% = toluene recovery rate of 98. 7% 'N-butyl dimethylamine recovery rate It was 98.7%. Then, the particles were obtained in the same manner as in the examples to obtain diphenyl ether oligomer particles, and no solids adhered in the solidification tank. 50 weights were used in the cleaning liquid of the particles obtained from the piano. In addition to the % sterol aqueous solution, the remaining amount was 312 ΧΡ / invention specification (supplement) / 96-09/96118689 25 200804460. The yield was 98%, and the number was washed and dried in the same manner as in Example i, and the average molecular weight was 3,440. The liquid component separated by solid-liquid separation and the methanol water discharged from the washed particles = force 25 mm in diameter, theoretical tower The batch steaming hall is carried out under the conditions of several μ, the temperature of the top of the tower and the temperature of the second pressure, and the methanol is further in the range of (4):=2 Γ, °°, and then continues with the conditions of the top temperature 28~ and the top latitude 15i) t°rr. Carry out the base, take care of the drunkenness/water/:# and then use the conditions of the top temperature of 91~9, the top of the tower to reduce the degree of m-machi, and the recovery of α85% to obtain more than 99% by volume of the water-soluble organic solvent. Methylacetamide. (Example 3) In the same manner as in Example i, except that the temperature (heat medium temperature) was changed to 60 Torr, the continuous distillation was carried out in the same manner as in Example i. A solution of diphenyl ether oligomer n, n-dimercaptoacetamide. On the average of 6 hours, the feed amount was 2〇6g/hr, the amount of φ part taken out was 80g/hr, the reflux ratio was 〇·35, and the residence time in the kettle was 4 9 hours. The diphenyl ether oligomer concentration was 丨7.9% by weight, and the residual amount of toluene was 1.1% by weight based on the isopropyl ether oligomer. Then, in the same manner as in Example 1, the diphenyl ether oligomer particles were obtained. There is no solid attachment in the solidification tank, the yield is 98%, and the number average molecular weight is ι〇〇2. (Example 4) In the same manner as in Example 1, except that the enthalpy temperature was changed to 1600 ° C and the overhead pressure degree was changed to 200 Torr, diphenyl was obtained in the same manner as in Example 1. A solution of the ether oligomer N,N-dimercaptoacetamide. 312XP/Invention Manual (Supplement)/96-09/96118689 26 200804460 On an average of 6 hours, the feed amount is 200g/hr, the bottom take-out amount is g/hr, and the reflux ratio is 〇.52. The time is 4 7 hours. 2# The oligomer concentration is 20.9% by weight, the residual amount of benzene is lower than that of diphenyl ether; ‘the content is 0.4% by weight. Then with the embodiment! In the same manner, the diphenyl-oligomer particles are obtained. There is no solid adhesion in the solidification tank, '99%, and the number average molecular weight is 998. (Example 5) In the first embodiment, except that the final temperature was 2 G (r (:, the atmosphere was set at the top of the column, the same was carried out in the same manner as in Example 1 to obtain a diphenyl duck). N,N-dimethylacetamide solution. On the average of , , and , the feed amount is 2 〇 lg / hr, the bottom withdrawal amount is (4) ^, and the residence time is 5.1 hours. The diphenyl bond is oligomeric. °;: ° / : ι ", the residual amount of toluene is 0.4 篁 relative to the di- phenyl ether oligomer, and then 'in the same manner as in the example i, = obtaining the diphenyl oligoparticles. The inside of the tank is Θ8%, and the number average molecular weight is 965. In the case of Kaowenwen (Synthesis Example 3) 2, in addition to toluene, the addition of toluene in the polymerization dad is added to the toluene solution obtained in Example 1, and no investment is made. In the same manner as in the synthesis example i, the m weight of the diphenylit oligomer was measured in the same manner as in the case of the synthesis example i, and a part of the same was carried out in the same manner as in the synthesis example 1. Drying, the number average molecular weight was 992.) ° (Example 6) 312 ΧΡ / invention specification (supplement) / 96-09/96118689 27 200804460 at lOO In the toluene solution of the diphenyl ether oligomer obtained in the synthesis example 3 of Og, the N,N-dimercaptoacetamide of 45 § § recovered in Examples 1 and 2 was added, and the theoretical column was 25 mm in diameter. Number of plates 15 (upper stage 7, lower stage 8), enthalpy temperature (heat medium temperature M15T:, top decompression degree chest rr conditions for continuous distillation 'to obtain diphenylit oligomer N, [dimethyl ethene amine 4重量%。 The average amount of the feed is 200g / hr, the amount of the bottom is 78g / hr, the reflux ratio is 0.24, the residence time in the kettle is 5. 〇 hours. The diphenyl ether oligomer ^ ^ is 20. 4% by weight 'The residual amount of toluene is 〇7 wt% with respect to the diphenyl sulfonate oligomer. A white turbid distillate is obtained from the top side of the distillation column. The mixture is allowed to stand still to obtain toluene 99 2 wt%, N. a mixed solution of 7 wt% of monobutyl dimethylamine and 0.05 wt% of water. The recovery of toluene was 98.6%, and the recovery of N-butyldimethylamine was 98 6%. Reciprocating and shrinking solidification tank with 400g of ion-exchanged water: a solution of 400g of diphenyl ether oligomer in N,N_:methylacetamide and granules in the solidification tank The aggregate of the diether oligomer particles was obtained without the solid adhesion. The obtained diphenyl ether oligomer particles were used, and the methanol recovered in Examples 1 and 2 was used for 1〇〇. The 〇g is washed with a 3 % by weight aqueous methanol solution, and dried in a vacuum dryer for 24 hours to obtain a yield of diphenyl (tetra) polymer particles of (4) and a number average molecular weight of 1005. The components are mixed with the methanol water obtained by washing the obtained particles, and the batch is carried out under the conditions of a column diameter of 25, a theoretical number of plates of 21 3, a θ θ degree of 63 to 6 generations, and a top of the column at atmospheric pressure. 92% recovery yielded more than 98% by weight of the enzyme. Then, with the top of the roof 312 ΧΡ / invention instructions (supplement) / 96-09 / 96118689 28 200804460 temperature 28 ~ 6Gt:, the top of the decompression degree (four) of the conditions continue to carry out distillation, distillation of methanol / water / DMAC Thereafter, 99% by weight of a water-soluble organic solvent of dimercaptoacetamide was obtained at a recovery of 85% at a column top temperature of 91 to 93 t: and a topping degree of decompression of 7 Torr. (Comparative Example 1) One = 200 g of the diphenyl ether oligomer obtained in Synthesis Example i was added to a reciprocating agitation type solidification table with 4 ceramic particle-forming solvent to carry out the particles. Chemical. The particle-forming solvent used was methanol, ethanol, and Thai propanol. Even with the use of the granule-forming solvent, the diphenyl ether oligomer becomes a part of the viscous cohesive material and adheres to the stirring wing and the wall of the solidification tank. The solidified tank was washed with a particleizing solvent, and the diphenyl ether oligomer particles were recovered on one side. The yield was 78%, the number average molecular weight was 1237, and the low molecular weight body was dissolved in the particleizing solvent to be eluted and lost. (Comparative Example 2) • In the same manner as in Comparative Example 1, except that the benzene solution of the diphenyl ether oligomer obtained in Synthesis Example 2 was used, the granulation was carried out. Even with any particleizing solvent, a portion of the diphenyl ether oligomer becomes a dissolved dope and adheres to the agitating wing and the wall of the solidification tank. The solid solution tank was washed with a particleizing solvent to recover the diphenyl ether oligomer particles. The yield was 81%, the number average molecular weight was 3848, and the low molecular weight body was dissolved in the particleizing solvent to be eluted and lost. (Comparative Example 3) 'In a nitrogen atmosphere, a stirring device, a thermometer, a baffle plate, a 312XP/invention manual (supplement)/96-09/96118689 29 200804460 gas introduction pipe, exhaust gas cooling pipe, exhaust gas Adding 7390 g of 2,6-dimethylhydrazine, 89 kg of terpene, 47 kg of decyl alcohol, and 625 g of N-butyl to a 200 L jacketed polymer crucible of SUS316C - part SUS304) Diamine, 60 g of hydrazine, Ν'-di-t-butylethylenediamine, 51 g of cuprous bromide. Stirring was started, warm water was flowed in the jacket and the inside of the polymerization vessel was controlled at 40 °C. When the temperature was stable, the polymerization was started by blowing air at a concentration of 8.5 Nm3/hr and diluting the oxygen concentration to 8% with nitrogen. After 225 minutes from the start of the polymerization, the oxygen concentration of the exhaust gas began to increase by 1.0%, so the introduction of dilution air was stopped, and 47 kg of sodium edetate aqueous solution (with 380 g of sodium edetate) was terminated. polymerization. The organic phase and the aqueous phase were allowed to stand still in the polymerization dad to remove the aqueous phase, and 45 kg of ion-exchanged water was again introduced and stirred and mixed with the organic phase, followed by standing separation to separate the organic phase from the aqueous phase. This water washing operation was repeated twice to obtain a 7.6% by weight solution of polyphenylene ether. (A part of the benzene solution was concentrated and dried by an evaporator, and vacuum-dried at 120 ° C / 48 hours (vacuum gauge) in a box-shaped vacuum dryer. As a result, the polymerization yield was *99%, and the number average molecular weight was 14,000. To 1000 g of the obtained polyphenylene ether-based benzene solution was added 310 g of N,N-dimercaptoacetamide, and it was found that the solution was suspended and a part of the viscous material was precipitated. Further, it was directly fed to a distillation apparatus having a column diameter of 25 mm and a theoretical number of plates of 15 (upper stage 7 and lower stage 8), but the pump was stopped and solvent replacement was impossible. Therefore, a part of the suspended toluene-dimethylacetamide solution was placed in an eggplant-shaped flask, and the solvent was easily replaced in the evaporator, but it became a higher viscosity at the same time as the distillation of the benzene. Turbid liquid, can not take it 312XP / invention manual (supplement) /96-09/96118689 30 200804460
312ΧΡ/發明說明書(補件)/96-09/96118689 31312ΧΡ/Invention Manual (supplement)/96-09/96118689 31
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| US8859646B2 (en) * | 2012-02-28 | 2014-10-14 | Sabic Global Technologies B.V. | Poly(phenylene ether) process |
| EP3390491B1 (en) | 2015-12-16 | 2021-03-03 | SHPP Global Technologies B.V. | Method for isolating a phenylene ether oligomer composition and phenylene ether oligomer composition |
| JP7021023B2 (en) * | 2018-07-27 | 2022-02-16 | 旭化成株式会社 | Manufacturing method of polyphenylene ether resin |
| KR102656211B1 (en) * | 2021-04-12 | 2024-04-15 | 주식회사 신아티앤씨 | Poly phenylene ether resin mixture |
| KR102652027B1 (en) * | 2021-04-12 | 2024-03-27 | 주식회사 신아티앤씨 | Poly phenylene ether resin composition |
| KR102595953B1 (en) * | 2021-04-12 | 2023-11-01 | 강남화성 (주) | Method for producing poly phenylene ether resin mixture |
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| JPS423195B1 (en) | 1964-02-24 | 1967-02-10 | ||
| GB1497293A (en) | 1974-02-11 | 1978-01-05 | Gen Electric | Preparation of polymer using copper catalysts |
| JPS54146896A (en) | 1978-05-10 | 1979-11-16 | Mitsubishi Gas Chem Co Inc | Recovery of polyphenylene oxide |
| JPH0811747B2 (en) | 1986-04-21 | 1996-02-07 | 住友化学工業株式会社 | Cyanate ester of polyphenylene oxide |
| JP3248424B2 (en) | 1996-02-29 | 2002-01-21 | 松下電工株式会社 | Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg |
| JP3261076B2 (en) | 1997-07-04 | 2002-02-25 | 日立化成工業株式会社 | Modified cyanate ester-based curable resin composition for laminate, prepreg and laminate using the same |
| JP4214336B2 (en) | 1999-03-30 | 2009-01-28 | 三菱瓦斯化学株式会社 | Method for producing polyphenylene ether resin powder |
| JP4288435B2 (en) * | 1999-03-30 | 2009-07-01 | 三菱瓦斯化学株式会社 | Method for producing polyphenylene ether resin |
| JP4736254B2 (en) | 2001-06-28 | 2011-07-27 | 三菱瓦斯化学株式会社 | Bifunctional phenylene ether oligomer and its production method |
| US6794481B2 (en) * | 2001-06-28 | 2004-09-21 | Mitsubishi Gas Chemical Company, Inc. | Bifunctional phenylene ether oligomer, its derivatives, its use and process for the production thereof |
| US6689920B2 (en) * | 2001-10-17 | 2004-02-10 | Mitsubishi Gas Chemical Company, Inc. | Bifunctional biphenyl and process for producing bifunctional phenylene ether oligomer compound using the same |
| JP3909838B2 (en) * | 2002-09-06 | 2007-04-25 | 旭化成ケミカルズ株式会社 | Production method of polyphenylene ether |
| US7193019B2 (en) * | 2003-10-22 | 2007-03-20 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of vinyl compound |
| JP4591665B2 (en) * | 2004-07-20 | 2010-12-01 | 三菱瓦斯化学株式会社 | Production method of vinyl compounds |
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| HK1132286A1 (en) | 2010-02-19 |
| JPWO2007139172A1 (en) | 2009-10-15 |
| WO2007139172A1 (en) | 2007-12-06 |
| EP2020425B1 (en) | 2013-07-31 |
| TWI413654B (en) | 2013-11-01 |
| US20090176962A1 (en) | 2009-07-09 |
| CN101479319A (en) | 2009-07-08 |
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| US7838618B2 (en) | 2010-11-23 |
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| KR20090020581A (en) | 2009-02-26 |
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